全 文 ：天然产物研究与开发 Nat Prod Res Dev 2012，24:869-872
文章编号:1001-6880(2012)07-0869-04
Received January 4，2012;Accepted March 22，2012
Foundation Item:Nationl key Basic Resarch Program(973)sub-project
(Nos． 2009CB522303 and 2011CB915503)
* Corresponding author Tel:86-871-5223058;E-mail:qinshizhao@ mail．
kib． com． cn;zhrpkm@ 163． com
肋果茶中的萜类化学成分研究
张兰春1，2，吴兴德2，何 隽2，彭丽艳2，张荣平1 * ，赵勤实2 *
1昆明医科大学药学院，昆明 650500;2 中国科学院昆明植物研究所
植物化学与西部植物资源持续利用国家重点实验室，昆明 650204
摘 要:从肋果茶(Sladenia celastrifolia)95%乙醇提取物的乙酸乙酯部位中分离得到 15 个萜类化合物，经波谱
学方法分别鉴定为 sladeniafolin A (1) ，grasshopper ketone (2) ，(3S，5R，6S，7E，9R)-7-megastigmene-3，6，9-triol
(3) ，hedytriol (4) ，(3S，5R，6R，7E，9R)-3，5，6，9-tetrahydroxy-7-megastigmene (5) ，1S* ，4R* -8-(4-hydroxy-2，
6，6-trimethylcyclohex-2-enyl)-6-methyloct-3E，5E，7E-trien -2-one (6) ，2α，3α，19α，23-tetrahydroxyurs-12-en-28-oic
acid (7) ，2α，3β，19α，23-tetrahydroxyurs-12-en-28-oic acid (8) ，pomolic acid (9) ，3-O-acetyl pomolic acid (10) ，urs-
aldehyde (11) ，camarolide (12) ，3β-hydroxyurs-11-en-13β(28)-olide (13) ，3β-hydroxy -11α，12α-epoxy-urs-13β，28-
olide (14)和 28-O-β-D-glucopyranosyl euscaphic acid (15)。以上化合物均首次从该植物中分离得到，其中 1 为
新的 C9 裂环烯醚萜。
关键词:肋果茶;裂环烯醚萜;倍半萜;三萜
中图分类号:R284． 2;Q946． 91 文献标识码:A
Terpenoids from Sladenia celastrifolia
ZHANG Lan-chun1，2，WU Xing-de2，HE Juan2，PENG Li-yan2，ZHANG Rong-ping1* ，ZHAO Qin-shi2*
1School of pharmaceutical science，Kunming 650500，China;2State Key Laboratory of Phytochemistry and Plant
Resources in West China，Kunming Institute of Botany，Chinese Academy of Sciences，Kunming 650204，China
Abstract:A new C9 seco-iridoid sladeniafolin A (1) ，together with fourteen known compounds were isolated from the
ethanol extract of Sladenia celastrifolia Kurz for the first time． On the basis of spectral data，the known compounds were i-
dentified as grasshopper ketone (2) ，(3S，5R，6S，7E，9R)-7-megastigmene-3，6，9-triol (3) ，hedytriol (4) ，(3S，5R，
6R，7E，9R)-3，5，6，9-tetrahydroxy-7-megastigmene (5) ，1 S* ，4 R* -8-(4-hydroxy-2，6，6-trimethylcyclohex-2-
enyl)-6-methyloct-3E，5E，7E-trien-2-one (6) ，2α，3α，19α，23-tetrahydroxyurs-12-en -28-oic acid (7) ，2α，3β，19α，
23-tetrahydroxyurs-12-en-28-oic acid (8) ，pomolic acid (9) ，3-O-acetyl pomolic acid (10) ，ursaldehyde (11) ，cama-
rolide (12) ，3β-hydroxyurs-11-en-13β(28)-olide (13) ，3β-hydroxy-11α，12α-epoxy-urs-13β，28-olide (14)and 28-O-
β-D-glucopyranosyl euscaphic acid (15)．
Key words:Sladenia celastrifolia;seco-iridoid;sesquiterpenoid;triterpenoid
Introduction
Sladenia celastrifolia Kurz (Sladeniaceae)is a mono-
typic species widely distributed in Burma，northern
Thailand，and the southern China［1］． Terpenoids have
been isolated from this plant ［2］． To discover more ter-
penoids，we initiated a phytochemical study on the
stems and leaves of S． celastrifolia． As a result，a new
seco-iridoid，sladeniafolin A (1)was isolated from this
plant，together with fourteen known terpenoids，grass-
hopper ketone (2)［3］，(3S，5R，6S，7E，9R)-7-me-
gastigmene-3，6，9-triol (3)［4］，hedytriol (4)［5］，(3S，
5R，6R，7E，9R)-3，5，6，9-tetrahydroxy-7-megastig-
mene (5)［6］，1S* ，4R* -8-(4-hydroxy-2，6，6-tri-
methylcyclohex-2-enyl)-6-methyloct-3E，5E，7E-trien-
2-one (6)［7］，2α，3α，19α，23-tetrahydroxyurs-12-en-
28-oic acid (7)［8］，2α，3β，19α，23-tetrahydroxyurs-
12-en-28-oicacid (8)［8］，pomolic acid (9)［9］，3-O-ac-
etyl pomolic acid (10)［10］，ursaldehyde (11)［11］，ca-
marolide (12)［12］，3β-hydroxyurs-11-en-13β(28)-ol-
ide (13)［13］，3β-hydroxy-11α，12α-epoxy-urs-13β，28-
olide (14)［14］，and 28-O-β-D-glucopyranosyl euscaph-
ic acid (15)［15］． Herein，we report the isolations and
structure elucidations of these compounds．
Fig. 1 Compounds 1-15 from S． celastrifolia
Experimental
General procedures
Optical rotation was measured on a Jasco P-1020 polar-
imeter． The IR spectrum was obtained with a Bruker
Tensor 27 spectrometer KBr disc． NMR spectra were
recorded on Bruker AM-400，DRX-500，and Avance III
600 spectrometers (δ in ppm，J in Hz)． ESI-MS spec-
tra were carried out on a Bruker HCT /Esquire spec-
trometer，HR-ESI-MS spectra on an API QSTAR Pulsar
spectrometer． Column chromatography (GC)was per-
formed using silica gel (100-200 and 200-300 mesh，
Qingdao Haiyang Chemical Co． Ltd，Qingdao，People’s
Republic of China) ，Lichropre RP-18 gel (40-63 μm，
Merck，Darmstadt，Germany) and MCI gel (75-150
μm，Mitsubishi Chemical Corporation，Japan) ，Frac-
tions were visualized by heating silica gel plates
sprayed with 10% H2SO4 in ethanol．
Plant Material
Stems and leaves of S． celastrifolia were collected in
Kumming Botanical Gardens of Yannan Province，P． R．
China，in July 2010． The plant was indentified by Prof．
X． Cheng at Kunming Institute of Botany． A voucher
specimen (No． 20100715)was deposited at the State
Key Laboratory of Photochemistry and Resources in
West China，Kunming Institute of Botany，Chinese A-
cademy of Sciences，R． P． China．
Extraction and Isolation
The air-dried plant material (28 kg)was percolated
with 95% EtOH (3 × 75 L，48 h)at room tempera-
ture． The extract was evaporated to dryness under re-
duced pressure． The obtained residue was suspended in
H2O and partitioned successively with EtOAc to afford
an EtOAc extract 1． 6 kg． The EtOAc extract was sub-
jected to column silica gel，which eluted gradiently with
petroleum ether:Me2CO (1 ∶ 0→0 ∶ 1)to afford five
fractions (1-5)．
Fraction 1 (10 g)was separated over silical gel col-
umn using petroleum ether:Me2CO (9 ∶ 1→3 ∶ 2)as
solvents to give 13 (50 mg)and 14 (10 mg)． Fraction
2 (20 g)was divided in to 2 subfractions (2a-2b)o-
ver silica gel column with petroleum ether:EtOAc (1∶
0→0 ∶ 1)as solvents． Subfraction 2a was further puri-
fied on silica gel column using petroleum ether:Me2CO
(8∶ 2→7∶ 3)and combined with sephadax LH-20 elu-
ted with CHCl3-MeOH (1∶ 1)to afford 11(10 mg)and
12 (2 mg)． Subfraction 2b with was chromatographed
further over MCI (85% MeOH-H2O to 100% MeOH)
give fraction 2b1 and 2b2． Subfraction 2b1 was purified
on a silica gel column eluted with petroleum ether:
Me2CO (8 ∶ 2)and than conbined with sephadax LH-
078 Nat Prod Res Dev Vol. 24
20 eluted with MeOH to afford 10 (10 mg) ，9 (9 mg)
and 6 (5 mg)． Subfraction 2b2 was applied to an RP-
18 gel eluted with MeOH-H2O (7∶ 3→1∶ 0) ，followed
by chromatographed over repeated silica gel CC and fi-
nally purified by sephadax LH-20 eluted with MeOH to
5 (30 mg)and 8 (10 mg)． Fraction 3 (10 g)was
separated over silica gel column and finally purified by
sephadax LH-20 column eluted with CHCl3-MeOH (1
∶ 1)to afforded 7 (30 mg)and 1 (29 mg)． 15(16
mg) ，4 (6 mg) ，3(30 mg)and 2(63 mg)were isola-
ted from fraction 4 (20 g)by chromatography on MCI
gel column (85% MeOH-H2O to 100% MeOH) ，and
repeated purified over silica gel CC，RP-18 and Sepha-
dex LH-20 columns．
Result and Discussion
Table 1 NMR data of compound 1 in CD3OD (δ in ppm，
J in Hz)
No． δH δC
1 4． 89，d，13． 2，Ha 72． 8，t
4． 69，d，13． 2，Hb
3 175． 3，s
4 2． 79，dd，6． 4，15． 8，Ha 35． 5，t
2． 64，dd，6． 0，15． 8，Hb
5 3． 13，m 30． 7，d
6 1． 74，m，Ha 38． 9，t
1． 63，m，Hb
7 3． 51，m，Ha 59． 6，t
3． 42，m，Hb
8 5． 71，t 128． 9，d
9 136． 6，s
10 4． 21，m，Ha 58． 7，t
4． 17，m，Hb
Fig. 2 Key 1H-1H COSY and HMBC correlations
Compound 1 was obtained as colorless oil． Its molecular
formula C9H14O4 was established by HR-ESI-MS (m/z
209． 0789［M + Na］+，calcd 209． 0789) ，indicating
three degrees of unsaturation． Its IR spectrum exhibited
absorption bands for hydroxy (3395 cm-1) ，ester car-
bonyl groups (1727 cm-1) ，and double band (1646
cm-1)． An analysis of the 1H NMR spectrum indicated
the typical signals of one olefinic protons at δ 5． 71
(1H，m)and six oxygenated methylene protons［δH 4．
89 (1H，d，J = 13． 2 Hz，H-1a) ，4． 69 (1H，d，J = 13．
2 Hz，H-1b) ，3． 51 (1H，m，H-7a) ，3． 42 (1H，m，H-
7b) ，4． 21 (1H，m，H-10a) ，4． 17 (1H，m，H-10b) ］．
The 13C NMR (DEPT)spectra of 1 showed two meth-
ylenes (δC 35． 5，C-4;38． 9，C-6) ，one methane (δC
30． 7，C-5) ，three oxygenated methylenes (δC 72. 8，C-
1;59． 6，C-7;58． 7，C-10) ，one trisubstituted double
bond (δC 128． 9，C-8;136． 6，C-9)and an ester car-
bonyl (δC 175． 3，C-3)． The above evidence implied
that compound 1 was a C9 seco-iridoid． Its 1D NMR da-
ta was similar to those of floribundane B［16］． The obvi-
ous differcnce was that the methyl group in floribun-
dane B was substituted by a hydroxymethyl group in 1，
which was supported by the 1D NMR data (Table 1)．
In addition，the ester carbonyl was substituted at C-3 in
1 rather than C-1 in floribundane B，as deduced from
the 1H-1H COSY correlations of H2-4 /H-5 /H2-6 /H2-
7，and confirmed by the HMBC correlations from H2-1，
H-4a (δH 2． 79，dd，J = 6． 4，15． 8 Hz) ，and H-4b (2．
64，dd，J = 6． 0，15． 8 Hz)to the ester carbonyl． The
ROESY correlation of H-8 with H-1a suggested the E-
orientation of the double bond in compound 1． On the
basis of the above evidence，compound 1 was deter-
mined to be a new C9 7，8-secoiridoid derivative and
named as sladenfolin A．
Sladeniafolin A (1) :colorless oil，C9H14 O4; ［α］
13． 1
D
-2． 18 (c 0． 67，CH3OH)． UV (CH3OH) :λmax(log
ε) :201 (3． 47)． IR (KBr) :3395，2935，2883，1727，
1384，1318，1296，1268，1087，1086，1055，1023
cm-1 ． 1H and 13C NMR:Tables 1，ESI-MS (positive) :
209 ( ［M + Na］+)． HR-ESI-MS (positive) :209．
0787( ［M + Na］+，C9H14O4Na;calc． 209． 0789)．
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